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WO2018105539A1 - Électrode négative pour batteries secondaires à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux - Google Patents

Électrode négative pour batteries secondaires à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2018105539A1
WO2018105539A1 PCT/JP2017/043396 JP2017043396W WO2018105539A1 WO 2018105539 A1 WO2018105539 A1 WO 2018105539A1 JP 2017043396 W JP2017043396 W JP 2017043396W WO 2018105539 A1 WO2018105539 A1 WO 2018105539A1
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Prior art keywords
negative electrode
positive electrode
carbon material
graphite
binder
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PCT/JP2017/043396
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English (en)
Japanese (ja)
Inventor
康平 続木
貴志 神
史治 新名
柳田　勝功
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to JP2018554979A priority Critical patent/JP6883773B2/ja
Priority to CN201780070100.3A priority patent/CN109997253B/zh
Priority to US16/466,126 priority patent/US11005090B2/en
Publication of WO2018105539A1 publication Critical patent/WO2018105539A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a negative electrode for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery.
  • Patent Document 1 discloses a negative electrode for a non-aqueous electrolyte secondary battery using a polymer fiber such as a fibrillated cellulose fiber as a binder. Patent Document 1 describes that the adhesion of the composite material layer to the current collector is improved, and good cycle characteristics of the battery can be obtained.
  • a negative electrode for a nonaqueous electrolyte secondary battery which is one embodiment of the present disclosure includes a negative electrode current collector and a negative electrode mixture layer formed on the negative electrode current collector.
  • the negative electrode composite layer includes graphite, a carbon material having a BET specific surface area larger than that of the graphite and 10 m 2 / g or more, and a hydrophobic binder, and the binder on the particle surface of the carbon material.
  • the coverage of the binder is higher than the coverage of the binder on the surface of the graphite particles.
  • a nonaqueous electrolyte secondary battery which is one embodiment of the present disclosure includes the above negative electrode, a positive electrode, and a nonaqueous electrolyte, and the positive electrode includes a first positive electrode active material, a second positive electrode active material, and a phosphate compound.
  • the first positive electrode active material has a pore volume of 100 mm or less and the volume per mass of the pores is 8 mm 3 / g or more, and the second positive electrode active material has a pore diameter of 100 nm or less.
  • the hit volume is 5 mm 3 / g or less.
  • the volume per mass of pores having a pore diameter of 100 nm or less in the first positive electrode active material is 4 times or more than the volume per mass of pores having a pore diameter of 100 nm or less in the second positive electrode active material. It is.
  • a non-aqueous electrolyte secondary battery having excellent input characteristics can be provided.
  • a negative electrode for a non-aqueous electrolyte secondary battery includes a carbon material (hereinafter referred to as “a carbon material”) having a BET specific surface area larger than that of graphite and 10 m 2 / g or more in addition to graphite and a hydrophobic binder.
  • the carbon material A functions as a negative electrode active material like graphite, and the coverage of the binder on the particle surface is higher than the coverage of graphite.
  • the graphite used as the negative electrode active material generally has a BET specific surface area of 10 m 2 / g or less, and many reaction points exist on the particle surface.
  • the distribution of the binder in the composite layer is simply uniform in order to improve the adhesion of the electrode plates (adhesion between the constituent materials of the composite layer and adhesion between the composite layer and the current collector). If the graphite particle surface is coated with a large amount of binder, the battery reaction is hindered and the input characteristics are deteriorated.
  • the carbon material A having a large specific surface area can use the inside of the particle for the battery reaction even if a large amount of the binder is adhered to the particle surface. Furthermore, the carbon material A covered with a large amount of the binder functions as a good adhesion point between the graphite particles, and improves the adhesion of the electrode plate. That is, according to the negative electrode for a non-aqueous electrolyte secondary battery that is one embodiment of the present disclosure, it is possible to significantly improve the input characteristics of the battery while sufficiently ensuring good adhesion of the electrode plate.
  • the nonaqueous electrolyte secondary battery 10 that is a cylindrical battery including a cylindrical metal case is illustrated, but the nonaqueous electrolyte secondary battery of the present disclosure is not limited thereto.
  • the nonaqueous electrolyte secondary battery of the present disclosure may be, for example, a rectangular battery including a rectangular metal case, a laminated battery including an exterior body made of a resin sheet, and the like.
  • the wound electrode body 14 is illustrated as an electrode body, the electrode body may be a stacked type in which a plurality of positive electrodes and a plurality of negative electrodes are alternately stacked via separators.
  • FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery 10.
  • the nonaqueous electrolyte secondary battery 10 includes an electrode body 14 having a winding structure and a nonaqueous electrolyte (not shown).
  • the electrode body 14 includes a positive electrode 11, a negative electrode 12, and a separator 13, and the positive electrode 11 and the negative electrode 12 are wound around the separator 13 in a spiral shape.
  • the one axial side of the electrode body 14 may be referred to as “upper” and the other axial direction may be referred to as “lower”.
  • the positive electrode 11, the negative electrode 12, and the separator 13 constituting the electrode body 14 are all formed in a long shape. These members are in a state of being alternately stacked in the radial direction of the electrode body 14 by being wound in a spiral shape.
  • the longitudinal direction of each electrode is the winding direction
  • the width direction of each electrode is the axial direction.
  • the positive electrode lead 19 that electrically connects the positive electrode 11 and the positive electrode terminal is connected to, for example, the longitudinal center of the positive electrode 11 and extends from the upper end of the electrode group.
  • the negative electrode lead 20 that electrically connects the negative electrode 12 and the negative electrode terminal is connected to, for example, the longitudinal end portion of the negative electrode 12 and extends from the lower end of the electrode group.
  • the case main body 15 and the sealing body 16 constitute a metal battery case that houses the electrode body 14 and the nonaqueous electrolyte.
  • Insulating plates 17 and 18 are provided above and below the electrode body 14, respectively.
  • the positive electrode lead 19 extends through the through hole of the insulating plate 17 toward the sealing body 16 and is welded to the lower surface of the filter 22 that is the bottom plate of the sealing body 16.
  • the cap 26 of the sealing body 16 electrically connected to the filter 22 serves as a positive electrode terminal.
  • the negative electrode lead 20 extends to the bottom side of the case main body 15 and is welded to the bottom inner surface of the case main body 15.
  • the case body 15 serves as a negative electrode terminal.
  • the case body 15 is a bottomed cylindrical metal container.
  • a gasket 27 is provided between the case main body 15 and the sealing body 16 to ensure hermeticity in the battery case.
  • the case main body 15 includes an overhanging portion 21 that supports the sealing body 16 formed by pressing a side surface portion from the outside, for example.
  • the overhang portion 21 is preferably formed in an annular shape along the circumferential direction of the case body 15, and supports the sealing body 16 on the upper surface thereof.
  • the sealing body 16 has a structure in which a filter 22, a lower valve body 23, an insulating member 24, an upper valve body 25, and a cap 26 are stacked in this order from the electrode body 14 side.
  • the members constituting the sealing body 16 have, for example, a disk shape or a ring shape, and the members other than the insulating member 24 are electrically connected to each other.
  • the lower valve body 23 and the upper valve body 25 are connected to each other at the center, and an insulating member 24 is interposed between the peripheral edges. Since the lower valve body 23 is provided with a vent hole, when the internal pressure of the battery rises due to abnormal heat generation, the upper valve body 25 swells toward the cap 26 and separates from the lower valve body 23, thereby electrically connecting the two. Blocked. When the internal pressure further increases, the upper valve body 25 is broken and the gas is discharged from the opening of the cap 26.
  • the positive electrode 11 includes a positive electrode current collector 11a and a positive electrode mixture layer 11b formed on the positive electrode current collector 11a.
  • a metal foil that is stable in the potential range of the positive electrode 11 such as aluminum, a film in which the metal is disposed on a surface layer, or the like can be used.
  • the positive electrode mixture layer 11b includes a positive electrode active material, a conductive material, and a binder.
  • the positive electrode 11 is formed by, for example, applying a positive electrode mixture slurry containing a positive electrode active material, a conductive material, a binder, and the like to both surfaces of the positive electrode current collector 11a, drying the coating film, and then compressing the positive electrode mixture layer. 11b can be formed on both sides of the current collector.
  • the positive electrode mixture layer 11b is formed over the entire area of both surfaces of the positive electrode current collector 11a excluding, for example, a portion where the positive electrode lead 19 is welded.
  • the thickness of the positive electrode mixture layer 11b is not particularly limited, but is preferably 30 ⁇ m to 150 ⁇ m on one side of the positive electrode current collector 11a.
  • the positive electrode active material include lithium-containing transition metal oxides containing metal elements such as Ni, Co, Mn, and Al. Note that one type of lithium-containing transition metal oxide or a plurality of types of lithium-containing transition metal oxides may be used for the positive electrode active material.
  • the positive electrode active material may have pores inside the particles, and the positive electrode mixture layer 11b may include first and second positive electrode active materials and phosphoric acid compounds having different pore volumes. Good.
  • a positive electrode active material containing many pores for example, decomposition products due to side reactions are likely to be generated, and a high-resistance film is formed on the surface of the negative electrode 12, but a hydrophobic bond is formed between the phosphate compound and the negative electrode 12.
  • the carbon material A to which a large amount of material is attached the formation of a high-resistance film can be suppressed.
  • the combination of the positive electrode active material containing many pores and the negative electrode 12 may further improve the input characteristics of the battery.
  • the first positive electrode active material has a pore volume (hereinafter referred to as “100 nm or less pore volume”) having a pore diameter of 100 nm or less per mass of the active material of 8 mm 3 / g or more.
  • the second positive electrode active material has a pore volume (100 nm or less pore volume) having a pore diameter of 100 nm or less per mass of the active material of 5 mm 3 / g or less.
  • the ratio of the pore volume of 100 nm or less in the first cathode active material to the pore volume of 100 nm or less in the second cathode active material (hereinafter referred to as “first / second pore volume ratio”) is 4 times or more. There may be.
  • the pore volume of 100 nm or less can be measured, for example, by the BJH method using a gas adsorption amount measuring device (manufactured by Cantachrome).
  • the content of the first positive electrode active material in the positive electrode mixture layer 11b is, for example, 30% by mass or less with respect to the total amount of the first and second positive electrode active materials.
  • the upper limit of the pore volume of 100 nm or less of the first positive electrode active material is not particularly limited, but is preferably 100 mm 3 / g or less.
  • the pore volume of 100 nm or less of the first positive electrode active material is preferably 10 mm 3 / g or more, more preferably 15 mm 3 / g or more.
  • the pore volume of 100 nm or less of the second positive electrode active material is preferably 3 mm 3 / g or less, more preferably 2 mm 3 / g or less.
  • the average particle diameter of the positive electrode active material (including the first and second positive electrode active materials; the same applies hereinafter) is, for example, 2 ⁇ m or more and less than 30 ⁇ m.
  • the average particle diameter of the positive electrode active material is a volume average particle diameter measured by a laser diffraction method, and means a median diameter at which the volume integrated value becomes 50% in the particle diameter distribution.
  • the positive electrode active material may be secondary particles formed by aggregation of primary particles.
  • the average particle diameter of the primary particles constituting the first positive electrode active material is 500 nm or less and smaller than the average particle diameter of the primary particles constituting the second positive electrode active material.
  • the average primary particle size was determined by randomly extracting 100 positive electrode active material particles observed with a scanning electron microscope (SEM), and calculating the average value of the major axis and minor axis length of each particle.
  • the diameter can be a value obtained by averaging the particle diameters of 100 particles.
  • a layered lithium transition metal oxide is used as the positive electrode active material.
  • the layered lithium transition metal oxide may contain elements other than Ni, Co, Mn, and Al, and may contain, for example, Zr.
  • the positive electrode active material is prepared by mixing, for example, a lithium-containing compound such as lithium hydroxide and an oxide obtained by firing a hydroxide containing a metal element M other than Li at a target mixing ratio. It can be synthesized by firing the mixture.
  • the pore volume of 100 nm or less of the first and second positive electrode active materials can be adjusted when preparing a hydroxide containing the metal element M.
  • the hydroxide is obtained, for example, by dropping an aqueous alkali solution such as sodium hydroxide into an aqueous solution containing a compound of the metal element M and stirring the solution. Adjust pH etc.
  • the average particle diameter of the primary particles can be adjusted by setting the firing temperature to 700 ° C. to 1000 ° C. for the first positive electrode active material and 800 ° C. to 1100 ° C. for the second positive electrode active material.
  • the phosphoric acid compound may be contained in the positive electrode mixture layer 11b, but is preferably present in a state of adhering to the surface of the first positive electrode active material, and phosphoric acid adhering to the particle surface of the first positive electrode active material
  • the ratio of the compound is set to be larger than the ratio of the phosphate compound adhering to the particle surface of the second positive electrode active material.
  • the content of the phosphoric acid compound in the positive electrode mixture layer 11b is, for example, 0.1% by mass to 5% by mass with respect to the total amount of the positive electrode active material.
  • the particle size of the phosphoric acid compound is preferably smaller than the particle size of the first and second positive electrode active materials, and is, for example, 50 nm to 10 ⁇ m.
  • the particle size of the phosphoric acid compound is a value obtained by randomly extracting 100 phosphoric acid compound particles observed with a scanning electron microscope (SEM), measuring the longest diameter of each particle, and averaging the measured values. .
  • the phosphoric acid compound contained in the positive electrode mixture layer 11b is not particularly limited as long as it is a compound containing phosphoric acid such as phosphoric acid and phosphate.
  • phosphoric acid such as phosphoric acid and phosphate.
  • lithium phosphate, lithium dihydrogen phosphate, cobalt phosphate, phosphorus examples thereof include nickel oxide, manganese phosphate, potassium phosphate, calcium phosphate, sodium phosphate, magnesium phosphate, ammonium phosphate, and ammonium dihydrogen phosphate. These may be used alone or in combination of two or more.
  • the phosphate compound may exist in the form of a hydrate. Among these, lithium phosphate is preferable, and trilithium phosphate (Li 3 PO 4 ) is particularly preferable.
  • Examples of the conductive material included in the positive electrode mixture layer 11b include carbon materials such as carbon black, acetylene black, ketjen black, and graphite.
  • Examples of the binder contained in the positive electrode mixture layer 11b include fluorine resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide resin, acrylic resin, and polyolefin resin. it can. These resins may be used in combination with cellulose derivatives such as carboxymethyl cellulose (CMC) or a salt thereof, polyethylene oxide (PEO), and the like.
  • CMC carboxymethyl cellulose
  • PEO polyethylene oxide
  • the negative electrode 12 includes a negative electrode current collector 12a and a negative electrode mixture layer 12b formed on the negative electrode current collector 12a.
  • the negative electrode current collector 12a has a thickness of 5 ⁇ m to 20 ⁇ m, for example.
  • a metal foil that is stable in the potential range of the negative electrode 12 such as copper, a film in which the metal is disposed on the surface layer, or the like can be used.
  • the negative electrode mixture layer 12b includes graphite, a carbon material (carbon material A) having a BET specific surface area larger than that of graphite and 10 m 2 / g or more, and a hydrophobic binder.
  • the negative electrode 12 is coated with a negative electrode mixture slurry containing graphite, a carbon material A, a binder, and the like on both surfaces of the negative electrode current collector 12a, dried, and then compressed to form a negative electrode mixture layer 12b. Can be formed on both sides of the current collector.
  • the negative electrode mixture layer 12b is formed over the entire area of both surfaces of the negative electrode current collector 12a excluding, for example, a portion where the negative electrode lead 20 is welded.
  • the thickness of the negative electrode mixture layer 12b is not particularly limited, but is preferably 30 ⁇ m or more on one side of the negative electrode current collector 12a, and more preferably 50 ⁇ m or more.
  • the thickness of the negative electrode mixture layer 12b is, for example, 30 ⁇ m to 150 ⁇ m.
  • the content of the carbon material A in the negative electrode mixture layer 12b is, for example, 20% by mass or less based on the total mass of graphite.
  • the content of the carbon material A is preferably 0.5% by mass to 15% by mass and more preferably 1% by mass to 10% by mass with respect to the total mass of the graphite.
  • the content of the carbon material A is, for example, 1% by mass to 10% by mass with respect to the total mass of the negative electrode mixture layer 12b.
  • the carbon material A having a large BET specific surface area tends to have a large irreversible capacity at the time of initial charge / discharge, and when the content of the carbon material A increases too much, the energy density of a reversibly usable battery decreases. There is.
  • the distribution of graphite, the carbon material A, and the binder in the negative electrode mixture layer 12b is substantially uniform.
  • the negative electrode mixture layer 12b is divided into two at the center in the thickness direction, the content of the carbon material A on the negative electrode current collector 12a side with respect to the content of the carbon material A on the surface side of the negative electrode mixture layer 12b The ratio is 0.9 to 1.1.
  • the graphite reversibly absorbs and releases lithium ions and functions as a negative electrode active material.
  • the graphite may be either natural graphite or artificial graphite.
  • the average particle diameter of graphite is, for example, 10 ⁇ m to 30 ⁇ m, or 15 ⁇ m to 30 ⁇ m, and is preferably larger than the average particle diameter of the carbon material A.
  • the average particle diameter of graphite is a volume average particle diameter measured by a laser diffraction method, and means a median diameter at which the volume integrated value is 50% in the particle diameter distribution (also about the average particle diameter of the carbon material A). The same).
  • the graphite those having a BET specific surface area of 15 m 2 / g or less are used, and generally those having a BET specific surface area of 10 m 2 / g or less are used.
  • a suitable example of the BET specific surface area of graphite is 1 m 2 / g to 10 m 2 / g.
  • the BET specific surface area of graphite is smaller than the BET specific surface area of the carbon material A, and graphite has many reaction points on the particle surface.
  • the BET specific surface area of graphite is the surface area per mass of graphite measured by the BET method, and can be measured using a BET specific surface area measuring device (“Tristar II 3020” manufactured by Shimadzu Corporation) by nitrogen adsorption / desorption ( The same applies to the BET specific surface area of the carbon material A).
  • the carbon material A like graphite, reversibly absorbs and releases lithium ions and functions as a negative electrode active material.
  • the carbon material A has carbon as a main component and has a BET specific surface area larger than that of graphite and 10 m 2 / g or more.
  • suitable carbon material A include carbon black, acetylene black, ketjen black and the like. A large amount of the carbon material A exists between the graphite particles in the negative electrode mixture layer 12b, for example.
  • the average particle diameter of the carbon material A is preferably 5 ⁇ m or more, and more preferably 10 ⁇ m or more.
  • the average particle size of the carbon material A is, for example, 5 ⁇ m to 20 ⁇ m, which is smaller than the average particle size of graphite. If the average particle diameter of the carbon material A satisfies the conditions, the carbon material A is likely to exist between the graphite particles, and it becomes easy to ensure good adhesion of the electrode plate.
  • the carbon material A may be secondary particles formed by agglomerating primary particles.
  • the average particle diameter of the primary particles is, for example, 0.01 ⁇ m to 1 ⁇ m. In the present specification, secondary particles mean particles that are not separated into primary particles even when ultrasonic vibration is applied.
  • the BET specific surface area of the carbon material A is 10 m 2 / g or more, preferably 20 m 2 / g or more, more preferably 30 m 2 / g or more.
  • the upper limit value of the BET specific surface area of the carbon material A is not particularly limited, but is 100 m 2 / g in consideration of, for example, battery capacity and cycle characteristics.
  • the carbon material A preferably has more pores than graphite inside the particle, and the average pore diameter is preferably 1 ⁇ m or less. An example of a suitable average pore diameter is 0.1 ⁇ m to 1 ⁇ m.
  • the pores of the carbon material A are formed, for example, between primary particles constituting the secondary particles.
  • the graphite and the carbon material A may be contained in the negative electrode mixture layer 12b as a negative electrode active material, and other negative electrode active materials other than graphite and the carbon material A may be contained.
  • a metal alloyed with lithium such as silicon (Si) or tin (Sn), or an oxide containing a metal element such as Si or Sn (for example, silicon oxide represented by SiO x ) Etc.
  • the BET specific surface area of the material is preferably smaller than the specific surface area of the carbon material A and 15 m 2 / g or less. Further, the content is preferably less than that of graphite.
  • the hydrophobic binder (hereinafter referred to as “binder B”) included in the negative electrode mixture layer 12b is composed of a hydrophobic resin that does not dissolve in water.
  • the difference in the HSP value between the binder B and water is, for example, 10 or more.
  • the HSP value is a solubility index calculated by the three parameters of London dispersion force, dipole force, and hydrogen bond force.
  • the solubility is predicted by the sum of the differences between the solvent and solute parameters. It is assumed that the larger the sum of the differences, the smaller the solubility.
  • the negative electrode mixture layer 12b may contain CMC or a salt thereof, polyacrylic acid (PAA) or a salt thereof, polyvinyl alcohol (PVA), or the like.
  • the binder B may be any material as long as it adheres favorably to the particle surfaces of graphite and carbon material A, which are negative electrode active materials, and to the negative electrode current collector 12a.
  • high styrene rubber, ethylene propylene rubber, butyl rubber A rubber binder such as chloroprene rubber, butadiene rubber, isoprene rubber, styrene butadiene rubber (SBR), acrylonitrile butadiene rubber, acrylonitrile rubber, fluorine rubber, acrylic rubber, or silicone rubber can be used.
  • SBR is contained in the binder B, and the binder B may be comprised only by SBR substantially.
  • the binder B such as SBR is present in the form of particles having a particle size of 1 ⁇ m or less on the particle surfaces of graphite and carbon material A, for example. Since the binder B hardly penetrates inside the particles of the carbon material A, even if a large amount of the binder B adheres to the particle surface of the carbon material A, the inside of the particles of the carbon material A can be used for the battery reaction.
  • the coverage of the binder B on the particle surface of the carbon material A is higher than the coverage of the binder B on the graphite particle surface.
  • the coverage of the binder B is the ratio of the area covered by the binder B to the total area of the surfaces of the carbon material A and graphite particles. That is, the ratio of the area where the binder B adheres on the particle surface is carbon material A> graphite.
  • the presence of the binder B can reduce the useless binder B on the surface of the graphite particles that does not contribute to the improvement of the adhesion of the electrode plate, thereby improving the input characteristics of the battery.
  • the graphite particles can be strongly bonded to each other and the graphite particles and the negative electrode current collector plate can be strongly bonded by the carbon material A that is covered with a large amount of the binder B and exists between the graphite particles.
  • the coverage of the binder B on the particle surface of the carbon material A is determined by dyeing the negative electrode mixture layer 12b with a dye such as bromine and then scanning the surface of the negative electrode mixture layer 12b with a scanning electron microscope / energy dispersive X-ray. It can be observed and measured by spectroscopy (SEM / EDX) (the same applies to the coverage of graphite). By SEM / EDX observation, the total area of the particle surface of the carbon material A and the area of the portion of the particle surface of the carbon material A to which the binder B is attached are measured, and the coverage of the binder B is determined. calculate.
  • binder coverage ratio The ratio of the coverage of the binder B on the graphite particle surface to the coverage of the binder B on the particle surface of the carbon material A (hereinafter referred to as “binder coverage ratio”) is, for example, 0.9. Or 0.8 or less.
  • a suitable example of the binder coverage ratio is 0.5 to 0.9, more preferably 0.7 to 0.9. If the binder coverage ratio is in this range, it becomes easy to achieve both good electrode plate adhesion and battery input characteristics.
  • the coverage of the binding material B on the particle surface of the carbon material A is, for example, 1% to 20%, preferably 1% to 10%.
  • the binder coverage ratio may not satisfy the above relationship for all graphite and carbon material A, but it is preferable that at least 50% of graphite and carbon material A satisfy the above relationship.
  • substantially all the graphite and carbon material A may have a binder coverage ratio of 0.7 to 0.9.
  • the carbon material A and the binder B are mixed in advance in the preparation of the negative electrode mixture slurry, and the binder B is carbon material before graphite.
  • grain surface of A can be illustrated.
  • graphite is added to prepare a negative electrode mixture slurry.
  • the share during mixing may be increased, and the amount of binder B added may be increased.
  • mixing in a state where the solid content concentration is increased with a small amount of the dispersion medium, or a high shear force such as a pressure type homogenizer or a thin film swirl type high speed mixer (for example, “Filmix” manufactured by PRIMIX) may be applied.
  • the share at the time of the said mixing may be made high by using the possible mixer.
  • the negative electrode mixture layer 12b has first and second layers formed in order from the negative electrode current collector 12a side, and the content of the carbon material A in the first layer is the carbon material in the second layer. You may make it higher than the content rate of A.
  • the content of the carbon material A on the surface side (second layer) of the negative electrode composite material layer 12b is the negative electrode current collector 12a side (first The content of the carbon material A in the layer) may be less than 90%.
  • a reaction decomposition product from the positive electrode 11 is deposited on the surface of the negative electrode mixture layer 12b, and a high-resistance film may be formed by the decomposition product and the binder B in some cases. In this case, the input characteristics of the battery may be further improved by lowering the content of the carbon material A to which a large amount of the binder B adheres on the surface side of the negative electrode mixture layer 12b.
  • the separator 13 a porous sheet having ion permeability and insulating properties is used. Specific examples of the porous sheet include a microporous thin film, a woven fabric, and a nonwoven fabric.
  • a material of the separator 13 an olefin resin such as polyethylene or polypropylene, cellulose, or the like is preferable.
  • the separator 13 may have either a single layer structure or a laminated structure. A heat-resistant layer containing a heat-resistant material may be formed on the surface of the separator 13.
  • the non-aqueous electrolyte includes a non-aqueous solvent and an electrolyte salt dissolved or dispersed in the non-aqueous solvent.
  • the non-aqueous solvent for example, esters, ethers, nitriles such as acetonitrile, amides such as dimethylformamide, and a mixed solvent of two or more of these can be used.
  • the non-aqueous solvent may contain a halogen-substituted product in which at least a part of hydrogen in these solvents is substituted with a halogen atom such as fluorine.
  • esters examples include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate, dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC), and methyl propyl carbonate.
  • Chain carbonates such as ethyl propyl carbonate and methyl isopropyl carbonate
  • cyclic carboxylic acid esters such as ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL), methyl acetate, ethyl acetate, propyl acetate, methyl propionate (MP )
  • chain carboxylic acid esters such as ethyl propionate.
  • ethers examples include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,4 -Cyclic ethers such as dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineol, crown ether, 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether , Dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, diphen
  • a fluorinated cyclic carbonate such as fluoroethylene carbonate (FEC), a fluorinated chain carbonate, a fluorinated chain carboxylate such as methyl fluoropropionate (FMP), or the like.
  • FEC fluoroethylene carbonate
  • FMP fluorinated chain carboxylate
  • FEC fluoroethylene carbonate
  • FMP fluorinated chain carboxylate
  • the electrolyte salt is preferably a lithium salt.
  • the lithium salt LiBF 4, LiClO 4, LiPF 6, LiAsF 6, LiSbF 6, LiAlCl 4, LiSCN, LiCF 3 SO 3, LiCF 3 CO 2, Li (P (C 2 O 4) F 4), LiPF 6-x (C n F 2n + 1 ) x (1 ⁇ x ⁇ 6, n is 1 or 2), LiB 10 Cl 10 , LiCl, LiBr, LiI, lithium chloroborane, lithium lower aliphatic carboxylate, Li 2 B Borates such as 4 O 7 , Li (B (C 2 O 4 ) 2 ), Li (B (C 2 O 4 ) F 2 ), LiN (SO 2 CF 3 ) 2 , LiN (C 1 F 2l + 1 SO 2) (C m F 2m + 1 SO 2) ⁇ l, m is an integer of at least 1 ⁇ , and the like imide salts such as.
  • lithium salts may be used alone or in combination of two or more.
  • LiPF 6 is preferably used from the viewpoints of ion conductivity, electrochemical stability, and the like.
  • concentration of the lithium salt is preferably 0.8 to 1.8 mol per liter of the nonaqueous solvent.
  • Example 1 [Production of positive electrode] 91 parts by mass of a lithium-containing transition metal oxide (positive electrode active material) represented by Li 1.067 Ni 0.464 Co 0.186 Mn 0.278 Zr 0.005 O 2 and 7 parts by mass of acetylene black Then, 2 parts by mass of polyvinylidene fluoride and an appropriate amount of N-methyl-2-pyrrolidone (NMP) were mixed to prepare a positive electrode mixture slurry. Next, the positive electrode mixture slurry was applied to both surfaces of a positive electrode current collector made of an aluminum foil having a thickness of 15 ⁇ m, and after the coating film was dried, the coating film was compressed to form a positive electrode mixture layer.
  • a lithium-containing transition metal oxide positive electrode active material represented by Li 1.067 Ni 0.464 Co 0.186 Mn 0.278 Zr 0.005 O 2
  • NMP N-methyl-2-pyrrolidone
  • the current collector in which the positive electrode mixture layer was formed on both sides was cut into a predetermined electrode size, and an aluminum lead was connected to a portion where the surface of the current collector was exposed to obtain a positive electrode.
  • the pore volume of 100 nm or less of the positive electrode active material was 2 mm 3 / g.
  • the negative electrode mixture slurry was applied to both surfaces of a negative electrode current collector made of a copper foil having a thickness of 10 ⁇ m, and after the coating film was dried, the coating film was compressed to form a negative electrode mixture layer.
  • the current collector in which the negative electrode mixture layer was formed on both sides was cut into a predetermined electrode size, and a nickel lead was connected to a portion where the surface of the current collector was exposed to obtain a negative electrode.
  • the thickness of the negative electrode in the portion where the negative electrode composite material layer is formed is 60 ⁇ m, and the current collection with respect to the carbon material A content on the surface side of the composite material layer when the negative electrode composite material layer is divided into two at the center in the thickness direction
  • the ratio of the carbon material A content on the body side was 1.1.
  • the ratio of the SBR coverage on the graphite particle surface to the SBR coverage on the carbon black particle surface was 0.8.
  • the SBR coverage ratio was determined by SEM / EDX observation after dyeing the negative electrode mixture layer.
  • Carbon black is a secondary particle formed by agglomeration of primary particles, and has a volume average particle diameter measured by a laser diffraction method.
  • a laser diffraction particle size distribution measuring apparatus (“LA-960” manufactured by Horiba, Ltd.)
  • the average particle diameter (median diameter at which the volume integrated value becomes 50% in the particle diameter distribution. The same applies to graphite below) was 0.2 ⁇ m.
  • the average particle diameter of the graphite measured by the same method was 13 ⁇ m.
  • ethylene carbonate (EC) and dimethyl carbonate (DMC) were mixed at a volume ratio of 3: 7.
  • LiPF 6 was dissolved in the mixed solvent to a concentration of 1 mol / L to prepare a non-aqueous electrolyte.
  • the positive electrode and the negative electrode were wound in a spiral shape through a separator made of a polyethylene microporous film to produce a wound electrode body.
  • the electrode body is housed in a bottomed cylindrical battery case body under a nitrogen atmosphere, and after injecting the non-aqueous electrolyte, the opening of the battery case body is sealed with a gasket and a sealing body to form a cylindrical non-water An electrolyte secondary battery was produced.
  • Example 2 A negative electrode and a non-aqueous electrolyte secondary battery were produced in the same manner as in Example 1 except that carbon black having a BET specific surface area of 38 m 2 / g and an average particle diameter of 10 ⁇ m was used as the carbon material A.
  • Example 3 A first slurry and a negative electrode mixture slurry were prepared in the same manner as in Example 1 except that the blending amount of carbon black was 3 parts by mass, and a 40 ⁇ m thick first electrode was formed on both sides of the negative electrode current collector made of copper foil. 1 negative electrode mixture layer was formed. Subsequently, a first slurry and a negative electrode mixture slurry were prepared in the same manner as in Example 1 except that the amount of carbon black was 1 part by mass, and the thickness was 40 ⁇ m on the first negative electrode mixture layer. The second negative electrode mixture layer was formed. Then, in the same manner as in Example 1, a negative electrode and a nonaqueous electrolyte secondary battery were produced. The thickness of the negative electrode was 60 ⁇ m, and the carbon material content ratio was 0.7.
  • Example 4 A negative electrode and a non-aqueous electrolyte secondary battery were produced in the same manner as in Example 1 except that the following two types of positive electrode active materials and trilithium phosphate were used as the positive electrode active material.
  • Each positive electrode active material is a lithium-containing transition metal oxide represented by the following.
  • the content ratio of the first positive electrode active material to the total amount of the first positive electrode active material and the second positive electrode active material is 10% by mass, and the content of trilithium phosphate is the first positive electrode active material A1 and the second positive electrode. It was 2 mass% with respect to the total amount of active material B1.
  • the negative electrode and the non-aqueous electrolyte secondary were prepared in the same manner as in Example 1, except that an appropriate amount of water was blended and mixed at a peripheral speed of 1.5 m / s using a homodisper to prepare a negative electrode mixture slurry. A battery was produced.
  • Example 2 The negative electrode and the non-aqueous electrolyte secondary were the same as in Example 1 except that scaly carbon having a BET specific surface area of 8.3 m 2 / g was used instead of carbon black having a BET specific surface area of 39 m 2 / g. A battery was produced.
  • Table 1 shows the BET specific surface area of graphite and carbon material A together with the evaluation results.
  • the battery was charged with a current density of 0.2 It to half the rated capacity. Thereafter, charging was performed at a constant current density for 10 seconds, and the voltage at the time when charging for 10 seconds was completed was measured. The voltage is measured by changing the current density in the range of 0.2 to 1.5 It, and the measured voltage is plotted with each current density to obtain a voltage-current line. The voltage is 4.3 V from this line. The current value was calculated. The obtained current value of 4.3V and the voltage value of 4.3V were multiplied to obtain the value of the input characteristic.
  • the batteries of Examples 1 to 4 are superior in input characteristics as compared with the batteries of Comparative Examples 1 and 2. This is because the influence of inhibiting the charging / discharging reaction by the binder is reduced by covering the carbon material more than the graphite. Since the carbon material having a high BET specific surface area has small pores on the surface where the binder cannot enter, even if the surface is covered with the binder, it is considered that charge / discharge reaction is possible inside.
  • Example 2 using a carbon material having a large secondary particle size, the number of small pores into which the binder cannot enter the surface increases, so that the number of portions where charge / discharge reaction is possible increases and the input characteristics are further improved. It is thought that it improved.
  • Example 3 in which the carbon material coated with the binder was disposed on the surface side portion less than the side portion of the negative electrode composite layer current collector, the decomposition product from the positive electrode was deposited on the surface of the negative electrode and bonded on the carbon material. It is considered that the input characteristics are further improved by suppressing the formation of a high-resistance film by reacting with the deposit.
  • Example 4 using a specific positive electrode active material having a positive electrode active material with a large pore volume and a positive electrode mixed with lithium phosphate, the input characteristics are improved by using the positive electrode active material with a large pore volume.
  • the decomposition product generated by the side reaction between the positive electrode active material and the electrolytic solution is changed by the catalytic action of lithium phosphate, so that the formation of a high-resistance film on the negative electrode surface is suppressed, and the input is further increased.
  • the characteristics are considered to have improved.

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Abstract

L'invention concerne une batterie secondaire à électrolyte non aqueux, comprenant : un corps d'électrode enroulé qui comprend une électrode positive, une électrode négative et un séparateur, et dans lequel l'électrode positive et l'électrode négative sont enroulées pour former un rouleau avec le séparateur intercalé entre elles ; et un électrolyte non aqueux. L'électrode négative comprend un collecteur d'électrode négative et une couche de mélange d'électrode négative qui est formée sur le collecteur d'électrode négative. La couche de mélange d'électrode négative contient du graphite, un matériau carboné qui possède une surface spécifique BET égale à 10 m2/g ou plus, ladite surface spécifique BET étant plus grande que celle du graphite, et un liant hydrophobe. La couverture des surfaces des particules de matériau carboné par le liant est supérieure à la couverture des surfaces des particules de graphite par le liant.
PCT/JP2017/043396 2016-12-08 2017-12-04 Électrode négative pour batteries secondaires à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux Ceased WO2018105539A1 (fr)

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CN201780070100.3A CN109997253B (zh) 2016-12-08 2017-12-04 非水电解质二次电池用负极及非水电解质二次电池
US16/466,126 US11005090B2 (en) 2016-12-08 2017-12-04 Negative electrode for non-aqueous electrolyte secondary batteries, and non-aqueous electrolyte secondary battery

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3958349A4 (fr) * 2019-04-19 2022-07-13 Panasonic Holdings Corporation Électrode négative pour batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
WO2022168233A1 (fr) * 2021-02-04 2022-08-11 株式会社 東芝 Batterie à électrolyte non aqueux et bloc-batterie

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12315937B2 (en) 2019-11-27 2025-05-27 Vehicle Energy Japan Inc. Electrode for secondary battery
JP7358229B2 (ja) * 2019-12-23 2023-10-10 パナソニックホールディングス株式会社 非水電解質二次電池用負極及び非水電解質二次電池
JP7372146B2 (ja) * 2019-12-26 2023-10-31 パナソニックホールディングス株式会社 非水電解質二次電池用負極、及び非水電解質二次電池
JP7349349B2 (ja) * 2019-12-26 2023-09-22 パナソニックホールディングス株式会社 非水電解質二次電池用負極、及び非水電解質二次電池
CN115280426B (zh) * 2020-03-31 2024-12-24 松下知识产权经营株式会社 固体电解质材料及使用了该固体电解质材料的电池
JP7766284B2 (ja) * 2020-09-30 2025-11-10 パナソニックＩｐマネジメント株式会社 電極、及び電極の製造方法
KR20220057125A (ko) * 2020-10-29 2022-05-09 에스케이온 주식회사 이차전지용 음극 및 이를 포함하는 이차전지

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1021925A (ja) * 1996-07-05 1998-01-23 Sumitomo Bakelite Co Ltd 非水電解液二次電池用電極フィルム
JP2004134304A (ja) * 2002-10-11 2004-04-30 Hitachi Maxell Ltd 非水二次電池および正極塗料製造方法
JP2011192620A (ja) * 2010-03-17 2011-09-29 Toyo Ink Sc Holdings Co Ltd リチウムイオン二次電池電極用カーボンブラック分散体の製造方法
JP2012015051A (ja) * 2010-07-05 2012-01-19 Hitachi Vehicle Energy Ltd リチウムイオン二次電池、及びリチウムイオン二次電池用負極
JP2012221568A (ja) * 2011-04-04 2012-11-12 Toyota Motor Corp 正極板の製造方法
WO2017056448A1 (fr) * 2015-09-30 2017-04-06 パナソニックＩｐマネジメント株式会社 Batterie secondaire à électrolyte non aqueux

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101127395A (zh) * 2006-08-15 2008-02-20 深圳市比克电池有限公司 一种锂二次电池负极及其制造方法
JP5594548B2 (ja) 2010-08-25 2014-09-24 トヨタ自動車株式会社 電池用電極の製造方法
JP6094797B2 (ja) * 2012-08-03 2017-03-15 株式会社Ｇｓユアサ リチウム二次電池用正極活物質、その製造方法、リチウム二次電池用電極、リチウム二次電池
JP6466161B2 (ja) * 2014-12-18 2019-02-06 オートモーティブエナジーサプライ株式会社 リチウムイオン電池用負極材料
CN107112499B (zh) * 2015-02-25 2021-02-26 三洋电机株式会社 非水电解质二次电池用负极和非水电解质二次电池
KR102411086B1 (ko) * 2016-08-24 2022-06-20 덴카 주식회사 전지용 카본 블랙, 전극용 도전성 조성물, 전지용 전극 및 전지

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1021925A (ja) * 1996-07-05 1998-01-23 Sumitomo Bakelite Co Ltd 非水電解液二次電池用電極フィルム
JP2004134304A (ja) * 2002-10-11 2004-04-30 Hitachi Maxell Ltd 非水二次電池および正極塗料製造方法
JP2011192620A (ja) * 2010-03-17 2011-09-29 Toyo Ink Sc Holdings Co Ltd リチウムイオン二次電池電極用カーボンブラック分散体の製造方法
JP2012015051A (ja) * 2010-07-05 2012-01-19 Hitachi Vehicle Energy Ltd リチウムイオン二次電池、及びリチウムイオン二次電池用負極
JP2012221568A (ja) * 2011-04-04 2012-11-12 Toyota Motor Corp 正極板の製造方法
WO2017056448A1 (fr) * 2015-09-30 2017-04-06 パナソニックＩｐマネジメント株式会社 Batterie secondaire à électrolyte non aqueux

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3958349A4 (fr) * 2019-04-19 2022-07-13 Panasonic Holdings Corporation Électrode négative pour batterie secondaire à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux
WO2022168233A1 (fr) * 2021-02-04 2022-08-11 株式会社 東芝 Batterie à électrolyte non aqueux et bloc-batterie
JPWO2022168233A1 (fr) * 2021-02-04 2022-08-11
JP7443579B2 (ja) 2021-02-04 2024-03-05 株式会社東芝 非水電解質電池及び電池パック

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